EA020294B1 - Crosslinkable and foaming polyester-polyurethane (hybrid) resin moulding compositions, with foaming characteristics for closed mould applications - Google Patents

Abstract

The invention concerns a crosslinkable and foaming polyester-polyurethane resin moulding composition, comprising an A component, comprising: A1) at least one poly-functional isocyanate compound, and A2) at least one free radical polymerisation initiator, a B component, comprising by weight: B1) 100 parts of at least one polyol resin comprising: B11) 50 to 80 parts of at least one ethylenically unsaturated polyester polyol, B12) 20 to 50 parts of at least one ethylenically unsaturated monomer, with B11) being the reaction product of: a) an acid component comprising: a1) at least one ethylenically unsaturated diacid, and a2) at least one saturated diacid with a1/a2 molar ratio so varying to have an unsaturation content in B11) from 0.25/1 to 5/1, and b) a diol component in excess with respect to component a), B2) from 0.01 to 1.1 parts of water, B3) optionally up to 35% of at least one hydroxy alkyl (meth)acrylate, B4) at least one catalyst of the isocyanate/hydroxyl reaction, B5) at least one accelerator for the free radical initiator decomposition, B6) at least one foam stabiliser, B7) optionally fillers and/or other additives the said composition being free of any primary or of secondary amine and of any polyol of low Mw chain extender. The invention further relates to a process of preparation and specific uses in light weight articles in sanitary, building or automotive uses.

Description

Glass fiber reinforced plastics (CBP) are well known for being suitable for a wide variety of industries and applications. These applications include construction, automotive / transportation, shipbuilding, chemical resistant equipment, and sanitary products. These products are valued for versatility in their formulation, processing and final application. The most commonly used resin matrix is an unsaturated polyester resin (IRI). However, these materials are not without drawbacks or limitations, which include to some extent the fragile nature of the resin matrix.

Polyester-polyurethane hybrid resins have been developed to address this drawback, as well as provide additional benefits related to the process and end use. The term hybrid describes a new type of polymer that is created by combining the chemical groups and properties of two different polymers, namely, the unsaturated polyester and polyurethane. Hybrid resins increase molecular weight and stiffness as they cure as a result of the urethane chain extension reaction that occurs between the hydroxyl end groups of the unsaturated polyester and isocyanate groups. Crosslinking occurs between the unsaturation in the polyester backbone and the styrene monomer, increasing stiffness and heat resistance. Thus, they obtain a unique combination of properties that cannot be achieved using either of the two polymers separately.

Polyurethanes are well known for their use as rigid elastomers and processed foams, flexible or inflexible, where the latter are often used in layered structures, giving them insulating properties. The closed cell structure of these foams, in addition to the insulating properties, reduces density and allows for inflexibility, avoiding excessive weight gain.

US 5344852 discloses a water-blown hybrid foam composition based on an unsaturated polyester-polyurethane compound with a water equivalent content of 25 to 150% of the OH total of the polyol as one component and a N00 to OH ratio of 0.5 to 2, preferably 0, 8 to 1.2, the presence of a chain extension agent, such as a diamine and / or polyol, is essential. Preferred densities of the disclosed foams vary from 16 to 160 g / l and can reach 560 g / l with a filler content of 50% by weight.

Although polyurethane foams based on saturated polyols, polyesters or polyethers are heavily used on an industrial scale, this does not happen with polyester foams for reasons including poor texture and inconsistent cellular structure. Some of the significant technical problems to be solved relating to saturated polyol based polyurethane foam technology relate to the additional crosslinking reaction that proceeds along a free radical path including the ethylene unsaturation of said unsaturated polyester. The question is the ability to track the proper order and speed of competing and sequential reactions in a foamable unsaturated crosslinkable system. Such a system includes a polyisocyanate component and an isocyanate-reactive component, including a polyol and water as a blowing agent. The first reaction is an exothermic reaction of water with a polyisocyanate giving gaseous carbon dioxide and a polyamine, then reacting with a polyisocyanate to form polyurea, a reaction competing with a urethane to form a polyol reaction with the specified polyisocyanate, and finally a free radical crosslinking reaction including the ethylene unsaturation induced heat release from previous reactions and decomposition of a free radical initiator. In fact, the technical problem to be solved is to create a reproducible, manufactured with high mechanical performance and lightweight molded product with a density in a given range. The solution of the present invention is to keep track of predetermined reaction conditions and pricing for the unsaturated composition during its formation. In fact, the water content and the ratio of isocyanate groups to the sum of hydroxyls are limited in a predetermined manner, while the composition does not contain components that contribute to chain extension, such as low molecular weight polyols and / or diamines.

The present invention further develops the concept of hybrid resins without the use of any chain extending polyol or diamine with the inclusion of a foaming element that reduces mass by at least 50% compared to an unfoamed product and enhances the stiffness and inflexibility properties in the density range of the final foam, in particular in the case of sanitary molded products or molded building materials, varying from 0.4 to 1.2 g / ml, more specifically from 0.6 to 0.8 g / ml with fillers up to 50%.

A first aspect of the invention relates to a specific moldable composition of a crosslinkable expandable unsaturated polyester-polyurethane resin.

The second and third objects relate to certain methods for producing a molded foam from at least one composition, as defined in the present invention.

An additional object relates to various applications of the specified expandable composition

- 1,020,294.

Finally, the invention also encompasses, as a last resort, finished products such as foamed materials and foamed products obtained from the composition or methods defined by the present invention.

Thus, a first aspect of the invention relates to a moldable composition of a crosslinkable, expandable, unsaturated polyester-polyurethane resin that is easily foamed upon curing to give molded articles. Specified moldable composition includes:

component A, including:

A1) at least one polyfunctional isocyanate compound and

A2) at least one free radical polymerization initiator;

component B, including by weight:

B1) 100 parts of at least one polyol resin, including:

B11) from 50 to 80 parts of at least one ethylenically unsaturated complex polyester polyol with a hydroxyl number in the range from 80 to 170 mg KOH / g,

B12) from 20 to 50 parts of at least one ethylenically unsaturated monomer copolymerizable with unsaturation of said unsaturated complex polyether polyol, wherein said polyester polyol B11) is a reaction product:

a) an acidic component comprising:

a1) at least one ethylenically unsaturated diacid selected from the group consisting of dicarboxylic acid, dianhydride, anhydride and derivatives thereof, and a2) at least one saturated diacid selected from the group consisting of dicarboxylic acid, dianhydride, anhydride and derivatives thereof moreover, the molar ratio a1) / a2) varies in the range from 0.25 / 1 to 5/1, preferably from 0.5 / 1 to 4/1,

b) the diol component in excess with respect to component a), wherein said polyester polyol B11) has a Mn in the range of 700 to 1250,

B2) from 0.01 to 1.1 parts of water, preferably from 0.05 to 1 part, acting as a foaming (foaming) component, by reaction with the specified polyfunctional polyisocyanate,

B3) optionally, at least one hydroxyalkyl (meth) acrylate in an amount corresponding to up to 35%, preferably up to 25% by weight, relative to the unsaturated monomers B12) + B3),

B4) at least one isocyanate / hydroxyl reaction catalyst,

B5) at least one decomposition accelerator of a free radical initiator,

B6) at least one foam stabilizer,

B7) optionally, fillers and / or other additives, said composition being free of any primary or secondary amine and polyol having a Mn of less than 200, or any other polyurethane chain extension.

The polyisocyanate A1) of the invention may have a functionality of at least 2, and more preferably 2 to 4. It may be aliphatic, or aromatic, or alicyclic. Examples of suitable polyisocyanates for the present invention include 4,4'-diphenylenemethylene diisocyanate (MB1), isophorone diisocyanate, naphthalenediisocyanate, 4,4 ', 4''triphenylmethanetriisocyanate, BE8MOBiB В®, BE8MOBiV Ν®, polymethylene isocyanethyl-dimethaniphenyl-dimethaniphenylpheni-dimethaniphenyl-dimethaniphenyl-dimethanodiophenyl -2.2 ', 5.5'-tetraisocyanate and / or mixtures.

In general, the molar ratio a2) / a1) can vary from 0.2 / 1 to 4/1, preferably from 0.25 / 1 to 2/1, which corresponds to the ratio a2) / a1), varying accordingly in the range from 0 25/1 to 5/1, and preferably from 0.5/1 to 4/1.

More specifically, in said polyol resin B1), said unsaturated polyester polyol B11) can either be a mixture of at least two different unsaturated polyester polyols, or it can be partially replaced by at least one vinyl ester oligomer (bearing residual secondary hydroxyls resulting from disclosure of the epoxy cycle during esterification). More specifically, up to 30% of said polyester B11) (in OH equivalents) could be replaced with said vinyl ester oligomer.

Preferably, said mixture of at least two different unsaturated polyester polyols comprises a first polyester polyol with a corresponding ratio a1) / a2) ranging from 1.7 / 1 to 2.3 / 1 and a second polyester polyol with a corresponding molar ratio a1) / a2) in the range of 0.9 / 1 to 1.4 / 1.

Said component a1) is maleic anhydride or fumaric acid, and said component a2) is isophthalic acid and / or terephthalic acid or anhydride.

In said complex polyether polyol B11) OH groups of component b) are present in global excess relative to the carboxy groups of component a), so that the final OH number of the indicated poly

- 2 020294 la B11) is in the range from 80 to 170, preferably from 90 to 160 mg KOH / g. The global excess of OH in the synthesis of the specified polyol B11) can be adjusted up to 30%.

The polyol component b) includes diols such as ethylene glycol (EC), diethylene glycol (ΌΕΟ), triethylene glycol (TEC), propylene glycol (PC), dipropylene glycol (ΌΡΟ), hydrogenated bisphenol A (HBPA), neopentyl glycol (ΝΡΟ), 2-methylpropi 1,3 (ΜΡΌ), 2-butyl-2-ethylpropane-1,3-diol (ΒΕΡΌ) and mixtures thereof, polyethylene glycols (or polyoxyethylene diols) and polypropylene glycols (or polyoxypropylene diols) with Μν from 200 to 400.

Preferably, the polyol component b) is a mixture of at least two diols, more preferably said mixture comprises at least one branched diol such as neopentyl glycol (ΝΡΟ), 2-methylpropanediol-1,3 (ΜΡΌ) or 2-butyl-2- ethylpropane-1,3-diol (ΒΕΡΌ), in addition to a linear diol such as ethylene glycol (EC), diethylene glycol (ΌΕΟ) or triethylene glycol (TEC).

Monomers B12) may have at least one ethylene unsaturation, more specifically, from 1 to 2 per molecule. As examples of suitable monomers, styrene and / or derivatives such as vinyl toluene (o-, m-, p-methyl styrene), divinylbenzene, diallyl phthalate, (meth) acrylic esters such as methyl (meth) acrylate, diethylene glycol (meth ) acrylate, dipropylene glycol di (meth) acrylate.

In addition to comonomers B12), hydroxylated monomers can be added to the composition, as determined according to component B3), which are hydroxylated methacrylic esters, more specifically, hydroxyalkyl (meth) acrylates, and they can be used to control either an equivalent molecular weight for unsaturation ( an increase in B3) means an increase in unsaturation and a decrease in the equivalent molecular weight by unsaturation), or they can be used to regulate the average OH function component b) in order to comply with the Masovko-MShet relationship, which predicts the conditions under which gelation does not occur (Mastoto1esi1ev, νοί. 9, 1976, p. 199-211). Suitable examples of B3) are hydroxyethyl (meth) acrylate (HE (M) A), hydroxypropyl (meth) acrylate (HP (M) A).

Preferably, the polyester-polyurethane composition of the present invention has a ratio in isocyanate equivalents of component A1) to the sum of hydroxyls (including active OH of water) of component B in the range of 1.5 / 1 to 1.8 / 1. Preferably, at least each polyester polyol chain is attached to the polyisocyanate molecule by at least two urethane bonds.

The ratio in equivalents of H ₂ O (active OH) to the sum of the active hydroxyls is preferably less than 0.30 (or 30%). The given choice of this ratio allows you to adjust the amount of gaseous CO ₂ generated by the reaction between water (component B2) and the specified polyisocyanate A1). This exothermic reaction gives a primary amine, which then reacts with the polyisocyanate to form a urea bond and CO2, which acts as an effective blowing agent, the water being a blowing agent precursor. More preferably, this equivalent water ratio should be in the range of 0.15 to 0.25 (or 15 to 25%).

According to one embodiment of the present invention, said composition comprises fillers B7), which may be selected from mineral fillers and, more specifically, from calcium carbonate and / or alumina trihydrate. The mass ratio of these fillers may vary in accordance with the target density (lower density generally means lower content of mineral fillers), but also depending on the target mechanical performance (better performance with a higher filler content). Therefore, a compromise must be found between density and mechanical performance. The mass content of the mineral fillers B7 can vary from 1 to 150 parts, preferably from 15 to 100 parts, relative to 100 parts of the polyol resin B1).

Catalysts B4) are suitable for activating the urethane formation reaction between the polyisocyanate component A1) and the polyol component B1) (more specifically, B11 polyester polyol). They can be catalysts based on amines or organometallic compounds. Suitable amine-based catalysts are pentamethyldiethylenetriamine, trimethylaminoethylethanolamine, метил-methylmorpholine, tetramethyl-1,4-butanediamine, Ν-methylpiperazine, dimethylethanolamine, dimethylaminoethoxyethanol, diethylethanolamine, triethylamine. Liquid catalysts such as dimethylaminoethoxyethanol are preferred.

Suitable catalysts based on organometallic compounds are dibutyltin dilaurate, dibutyltin oxide, dibutyltin di-2-ethylhexanoate or tin octanoate. Liquid catalysts such as ΌΒΤΌΕ (dibutyltin dilaurate) are preferred.

Suitable accelerators B5) for decomposition of the free radical initiator A2) may include: cobalt octanoate, divalent or trivalent acetylacetonate, vanadium naphthenate or octanoate or vanadium acetonate or tertiary aromatic amines such as diethyl or dimeti

- 3,020,294 laniline, dimethyl p-toluidine. Preferred are diethyl or dimethylaniline, dimethyl ptoluidine. Accelerators B5) are used in the presence of peroxide or hydroperoxide initiators, which decompose upon reduction with an accelerator acting as a reducing agent.

As free radical initiators A2), azo compounds such as ΑΙΒΝ and organic peroxides or hydroperoxides such as tert-butyl peroxybenzoate (TBPB), tert-butyl peroctoate (TBPO), benzoyl peroxide (BPO), methyl ethyl ketone peroxide (MEKRO), hydroper (SNRO), dicumyl peroxide (ISRO), acetoacetic peroxide. BPO is preferred.

Silicon-based surfactants (preferably) or non-ionic surfactants can be used as foam stabilizers B6).

Their mass content in the composition can vary from 0.05 to 1% wt./wt. relative to resin B1).

Another objective of the present invention relates to a method for producing a molded foam product from at least one composition of the invention, said method being injection reaction molding in a closed mold.

More specifically, this method of injection reaction molding may include the steps of:

ί) injection of components A and B of the specified mixed composition through the head of a dynamic mixer at a pressure of from 0.15 to 4 MPa to

i) partial filling of the mold at molding pressure equal to atmospheric pressure or partial vacuum, and up to ϊϊΐ) foaming and filling of the entire mold at the foaming pressure resulting from the reaction of said water B2) with said polyisocyanate A1) during curing (specified expandable mixture).

The time of the dynamic mixture in the specified dynamic mixer should preferably be more than 10 s, more preferably at least 15 s and up to 25 s. Preferably, composition A and B is served at a temperature close to the temperature of the mold, which may be in the range of 25 to 40 ° C.

Another method for producing a molded foam article is also covered by the invention, wherein said method comprises the steps of:

ί) casting the combined mixture A and B, preferably obtained using a dynamic mixer, in an open mold and subsequently ίί) putting the lid of said mold in its place to allow it to form foam and fill the entire mold with foaming pressure, resulting from the reaction of said water B2) with said polyisocyanate A1) during curing.

Another objective of the invention relates to the use of the composition of the present invention for the production of lightweight molded products, more specifically, with a density in the range from 0.4 to 1.2 g / ml and preferably from 0.6 to 0.8 g / ml.

Various applications of these molded foam products are possible, among which are sanitary products, such as shower trays, bathroom pipes or wash basins.

Other possible uses of these molded products obtained from the composition of the present invention are molded units for building materials and / or building materials, such as units of artificial stone or artificial marble or artificial concrete. In this context, in addition to their inherent light weight, providing them with suitability and greater ease in handling and lifting by builders and construction workers (the mass of parts is reduced by at least half), these materials can also cause additional interest in this areas (construction and erection of buildings) due to their ability to heat and / or sound insulation.

Other applications and uses of molded products include automotive panels, more specifically for commercial and agricultural vehicles, or applications for heat or sound insulation.

Foam, more specifically a foam having a density in the range from 0.4 to 1.2 g / ml, preferably from 0.6 to 0.8 g / ml, and obtained from a foamable composition, as defined in the present invention, is another object covered by the present invention.

The latter object relates to foamed molded products obtained by molding at least one moldable composition, as defined in the invention, in particular with a density in the range from 0.4 to 1.2 g / ml, preferably from 0.6 to 0, 8 g / ml

These foamed molded products may be sanitaryware products, such as shower trays, bathroom pipes, washbasins, or they may be molded units of building materials and / or building materials, such as artificial stone, artificial marble or artificial concrete.

- 4,020,294

Said foamed molded products may also include a gel-coated exterior (shower trays, tubing, washbasins, etc.). In this case, a gel coating, which may be based on an unsaturated polyester or acrylate resin composition, is first applied to the surface of the mold (using spray or brush technology) and then partially cured until the foamable composition of the invention is molded, foamed and cured.

As an alternative to a gel-coated surface, said foamed molded products may include a finish surface formed by an acrylic or LV8 polymer, where the molded foam adheres to the polymer.

Examples

Complex polyester polyol.

Reagents were loaded into a reaction boiler equipped with a stirrer, a thermocouple, a packed column, a refrigerator, and a receiver. The apparatus was placed in a heater with a heating jacket, and the reactions were carried out under an inert atmosphere of nitrogen. The reagents were slowly heated until the mixture could be mixed, and then heated until the temperature at the top of the column reached 100-102 ° C. Water was removed from the system at a maximum reaction temperature of 215 ° C until the required acid number was reached. The resin was cooled to 120 ° C, stabilized with hydroquinone, then added to sufficiently stabilized styrene (naphthoquinone) to obtain 70% solid material. Three examples of unsaturated polyether polyol compositions are described in detail in Table. one.

In the table. 2 gives examples of compositions obtained on the basis of polyol as one components.

Table 1

Composition B1 polyol resin

Polyol 1 Polyol 2 Polyol 3 Fumaric acid (molar parts) 0.67 Maleic Anhydride 0.67 0.55 Isophthalic acid 0.33 0.33 0.45 Ethylene glycol 0, 66 0.66 0, 66 Neopentyl glycol 0, 66 0.66 0.66 Styrene w / w % in B1 thirty thirty thirty Dibutyltin Oxide (ppm) 500 500 500 Hydroquinone (ppm) 150 150 150

Naphthoquinone (ppm) 75 75 75 Acid number (per solid) in mg KOH / g 3 5 5 Hydroxyl number (per solid) in mg KOH / g 110 130 115

Table 2 Component B: compositions

ΒΙ ΒΙΙ ΒΙΙΙ Βίν Polyol 1 (B1) fifty 25 25 25 Polyol 2 (B1) 25 Polyol 3 (B1) 25 25 Calcium Carbonate (B7) fifty fifty 45 45 Diethylaniline (B5) 0.2 0.1 0.1 0.1 Pentamethyldiethylenetriamine (B4) 0.1 Trimethylaminoethylethanolamine (B4) 0.1 Dibutyltin dilaurate (B4) 0.1 0.1 Dibutyltin Oxide (B4) 0.2 0.2 Water (B2) 0.5 0, 35 0.5 0.5 % H ₂ O / OH _{amount a} in (ratio in equivalents,%) 29% 22% 28.5% 27%

Component A.

I) 5 parts of benzoyl peroxide in powder (A2) were mixed in 95 parts of component Α1: ΜΌΙ in the form of Lirgap (® Μ200Κ from BA8P.

This ΜΌΙ has an SOF functionality of 31% w / w. (molecular weight N00: 42) and has in

- 5 020294 based on oligomers of high functionality (equivalent ISO index is 414 equivalents mg KOH / g).

II) 10 parts of benzoyl peroxide (BPO) in powder (A2) were mixed in 90 parts of component Α1: ΜΌΙ (Lirgaia! ® M200B).

Compositions and their properties.

The temperature of components A and B together with the instrument was adjusted to 25 ° C.

The components were mixed in a Co \\ 1s8 dispersant (tip speed 6 m / s) for 30 s, then fed into a closed steel testing instrument with a volume of the forming cavity of 1 l. The tool was clamped and after 20 minutes the parts were removed from the mold. Variants of the compositions and the implementation of the method are shown in table. 3.

Example 6 was prepared as follows.

Polyol 1 (250 g) and polyol 2 (250 g), both with a solids content of 70%, were mixed together on a laboratory stirrer. Diethylaniline (1.0 g), dibutyltin dilaurate (1.0 g) and water (3.5 g) were added to this mixture. After 20 minutes of mixing, 500 g of calcium carbonate (average particle diameter of 5 μm) was added and mixing was continued for 30 minutes.

This component B was connected to A1) in a ratio of 80:20 (initiating system BPO: benzoyl peroxide, as defined above). In the case of molded tiles, the loading of the material was based on achieving a backpressure of 50%, based on the free increase in volume.

The free increase density in volume is the obtained density of the foam, where the only resistance present is atmospheric pressure. It can be easily measured using Archimedes flasks.

Other examples 7-14 were obtained in a similar main way, as example 6, varying the parameters given in table. 3, such as the inclusion of diethyltoluene diamine (ΌΕΤΑ), increased water content, reduced hydroxyl number of the polyol base, increased hydroxyl number of the polyol base, and reduced isocyanate to hydroxyl ratio. The polyols of examples 7-12 were filled with 50% calcium carbonate. Examples 13 and 14 are typical examples of US patent 5344852: example 13 in the absence of diamine and example 14 in the presence of diamine, and correspond to 30% calcium carbonate based on component B.

Table 3

Compositions and their properties

Composition H ₂ O / OH _amount ,% N00 / ONsumma Diamine, and% OH number, base, mg KOH / g The density of the free increase in volume, g / ml Molded density, g / ml Bending Strength Ι8Ο 178 Bending modulus Ι8Ο 178 Shock resistance Example 6 22% 1.74 / 1 Not 120 0.38 0.60 40 MPa 2.0 GPa 5.5 N.m Example 7 (comparative) 22% 1.74 / 1 one% PETRA 120 0.36 0.88 23 1,5 3.2 N.m Example 8 (comparative) 40% 1.4 / 1 Not 120 0.29 0.44 10 0.5 1.4 N.m Example 9 26% 2.0 / 1 90 0.52 0.80 38 2.0 5.5 N.m Example 10 sixteen% 1.28 / 1 160 0.40 0.70 44 1,6 6.2 N.m Example 12 (comparative) 40% 1.4 / 1 1% ϋΕΤΠΑ 120 0.26 0.40 10 0.5 1.4 N.m Example 13 (comparative) 38% 1,2 / 1 167 0.18 0.34 nine 0.8 2.3 N.m Example 14 (comparative) 38% 1,2 / 1 1% ϋΕΤΠΑ 167 0.22 0.40 12 0.8 2.3 N.m

Notes.

It is seen that an increase in the ratio of water equivalents to the sum of hydroxyls above 30% reduces the density of the free increase in volume, but worsens the mechanical properties.

The presence of diamine, when the ratio of H ₂ O / OH _{amount is} below 30%, obviously has a negative effect. It is obvious that a very fast gelation time of these compositions worsens the flow in the mold.

In the range of hydroxyl number 90-160 mg KOH / g of the polyol base, good mechanical properties are retained.

Variants of molding conditions.

600 g of components A1) and B11) were combined in the ratios indicated in the table. 3.

The components were mixed in a Co \\ 1s8 dispersant (tip speed 6 m / s), then fed into a closed steel combined testing tool with a volume of the forming cavity of 1 l. The tool was clamped and after 20 minutes the parts were removed from the mold. Variants of the compositions and the implementation of the method are shown in table. 4.

- 6,020,294

Table 4

Forming conditions options

one 2 3 4 5 ΜϋΙ A1 / (mass, parts) fifteen twenty fifteen fifteen fifteen Polyol VP * (mass, parts) 85 80 85 85 85 PSO / OH _amount (OH in B) (ratio of equivalents) 1.25 1.74 1.25 1.25 1.25 Polyol temperature (° C) thirty thirty thirty 25 thirty Mixing time (from) twenty twenty twenty thirty 10 Tool temperature (° C) 35 35 twenty 37 35 Part Density (g / ml) 0.7 0.65 0.7 0.8 Changeable

Stability of part properties Smooth everywhere Smooth everywhere The lower part is deformed Change is gloss Crust at the base, wave markings Bending Strength (MPa) 40 35 thirty 35 fifteen Bending Modulus (GPa) 2.0 2,5 1.8 1.8 1,5

* ΒΙΙ corresponds to a mixture of polyols 1 and 3, as shown in table. 2.

The results show the sensitivity of the method to the mixing time and the temperature of the component / device.

Molding tests.

The resinous system was dosed by an injection machine based on a discharge pump with a dynamic mixer together with Α1 / ΒΙΙ components in a ratio of 1/4 by volume, which corresponds to 15/85 wt./wt.

The mixture was injected into a closed steel combination tool (cavity volume 6 L), pre-coated with a standard gel coating (Ро1усог 1го вргау), after 20 minutes the products were removed from the mold.

Claims (29)

CLAIM 1. A moldable composition of a crosslinkable and expandable polyester-polyurethane resin, comprising: component A, including: A1) at least one polyfunctional isocyanate compound and A2) at least one initiator of free radical polymerization; Component B comprising: B1) 100 parts of at least one polyol resin comprising: Β11) 50 to 80 parts of at least one ethylenically unsaturated polyester polyol with a hydroxyl number in the range of 80 to 170, which is either a mixture of at least two different unsaturated polyester polyols, or partially replaced by at least one vinyl ester oligomer, Β12) from 20 to 50 parts of at least one ethylenically unsaturated monomer copolymerized with unsaturation of said unsaturated polyester polyol, said polyether polyol B11) being the reaction product: a) an acidic component comprising: a1) at least one ethylenically unsaturated diacid selected from the group consisting of dicarboxylic acid, dianhydride, anhydride and their derivatives, and a2) at least one saturated diacid selected from the group consisting of dicarboxylic acid, dianhydride, anhydride and their derivatives , moreover, the molar ratio a1) / a2) varies from 0.25 / 1 to 5/1, b) the diol component in excess relative to component a), - 7 020294 and the specified complex polyetherpolyols B11) has a Mn in the range from 700 to 1250, B2) from 0.01 to 1.1 parts of water, acting as a foaming agent, B3) at least one isocyanate / hydroxyl reaction catalyst, B4) at least one accelerator decomposition of a free radical initiator, B5) at least one foam stabilizer, and this composition is free from any primary or secondary amine and polyol having M \ t less than 200, or any other extension of the polyurethane chain, where the ratio in equivalents of H ₂ O to the sum of active hydroxyls is less than 0.30. 2. The composition according to claim 1, characterized in that it additionally contains at least one hydroxyalkyl (meth) acrylate in an amount up to 35%, preferably up to 25 wt.%, Relative to the unsaturated monomers B12), and fillers and / or other additives . 3. The composition according to claim 1, characterized in that up to 30% of the specified polyester B11) is replaced by the specified vinyl ester oligomer. 4. The composition according to claim 1, characterized in that said mixture of at least two different unsaturated polyester polyols comprises a first polyester polyol with a corresponding ratio a1) / a2) in the range from 1.7 / 1 to 2.3 / 1 and the second complex polyetherpolyols with an appropriate molar ratio of A1) / A2) in the range from 0.9 / 1 to 1.4 / 1. 5. Composition according to any one of claims 1 to 4, characterized in that said component a1) is maleic anhydride or fumaric acid and said component A2) is isophthalic acid and / or terephthalic acid or anhydride. 6. Composition according to any one of claims 1 to 5, characterized in that the ratio in equivalents of the isocyanates of component A1) to the sum of the hydroxyls of component B is from 1.5 / 1 to 1.8 / 1. 7. Composition according to any one of claims 1 to 6, characterized in that the equivalent ratio of water is in the range from 0.15 to 0.25. 8. Composition according to any one of paragraphs.2-7, characterized in that the composition includes fillers selected from mineral fillers. 9. The composition according to claim 8, wherein the mineral fillers are calcium carbonate and / or aluminum oxide trihydrate. 10. A method of obtaining a molded foamed product of at least one composition according to any one of claims 1 to 9, characterized in that the method is injection-injection molding in a closed mold. 11. The method according to p. 10, characterized in that it includes the steps: ί) injecting components A and B of the specified composition through the head of a dynamic mixer at a pressure of from 0.15 to 4 MPa to i) partial filling of the mold at a molding pressure equal to atmospheric pressure, and up to ϊϊΐ) foaming and filling the entire mold at a foaming pressure resulting from the reaction of water B2) with polyisocyanate A1) during curing. 12. A method of obtaining a molded foamed product of at least one composition according to any one of claims 1 to 9, characterized in that the method includes the steps of: ί) casting the combined mixture of A and B into an open mold; and ίί) subsequently closing the lid of said mold to form a foam and fill the entire mold at a foam pressure resulting from the reaction of water B2) with polyisocyanate A1) during curing . 13. The use of at least one moldable composition according to any one of claims 1 to 9 for the production of lightweight molded products. 14. The use according to claim 13, characterized in that said articles have a density in the range from 0.4 to 1.2 g / ml. 15. The use according to claim 13 or 14, characterized in that said molded products are sanitary equipment products. 16. The application of item 13 or 14, characterized in that the said molded products are building materials or automotive panels. 17. Application under item 16, characterized in that the building materials are heat or sound insulating materials. 18. Foam, characterized in that it is obtained from the foamable composition according to any one of claims 1 to 9. 19. Foam, characterized in that it is obtained by the method according to any one of paragraphs. 10-12. 20. The foam material according to claim 18, characterized in that it has a density in the range from 0.4 to 1.2 g / ml. 21. Foamed molded product, characterized in that it is obtained by molding at least one moldable composition according to any one of claims 1 to 9. 22. Foamed molded product, characterized in that it is obtained by the method according to PP.10-12. - 8 020294 23. Foamed molded product according to p. 21, characterized in that it has a density in the range from 0.4 to 1.2 g / ml. 24. Foamed molded product according to any one of paragraphs.21-23, characterized in that it is sanitary equipment. 25. Foamed molded product according to paragraph 24, characterized in that it is a shower tray, a pipe for a bathroom, a washbasin. 26. Foamed molded product according to any one of paragraphs.21-23, characterized in that it is a molded part of building materials and materials for the construction of buildings or automotive panels. 27. Foamed molded product according to claim 26, characterized in that said building materials or materials for the construction of buildings are selected from artificial stone, artificial marble or artificial concrete. 28. Foamed molded product according to claim 27, characterized in that it includes a gel-coated exterior finish. 29. Foamed molded product according to claim 27, characterized in that said foamed molded product includes a finishing surface formed by an acrylic or ABS polymer.